CN104817755A - Vulcanized ethylene-octene copolymer waterproof coiled material and production method thereof - Google Patents
Vulcanized ethylene-octene copolymer waterproof coiled material and production method thereof Download PDFInfo
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- CN104817755A CN104817755A CN201510167074.9A CN201510167074A CN104817755A CN 104817755 A CN104817755 A CN 104817755A CN 201510167074 A CN201510167074 A CN 201510167074A CN 104817755 A CN104817755 A CN 104817755A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Abstract
The invention relates to a vulcanized ethylene-octene copolymer waterproof coiled material and a production method thereof. The vulcanized ethylene-octene copolymer waterproof coiled material comprises a base layer, the base layer takes the ethylene-octene copolymer as a main raw material, and other auxiliary materials comprise fast extruding furnace black, calcium carbonate, ultrafine powdered steatile, polyethylene glycol and an antioxidant. By taking 100 parts of the ethylene-octene copolymer as a reference, the vulcanized ethylene-octene copolymer waterproof coiled material comprises the following components by weight part: 50-110 parts of fast extruding furnace black, 30-70 parts of ultrafine powdered steatile, 5-10 parts of calcium carbonate, 20-60 parts of plasticizer, 2-10 parts of polyethylene glycol, 1-6 parts of dicumyl peroxide, 0.5-2.75 parts of cross-linking agent and 1-3 parts of antioxidant. The ethylene-octene copolymer is crosslinked by dicumyl peroxide, complete crosslinking of the molecular chain of the ethylene-octene copolymer waterproof coiled material can be realized, thermal stability performance of the waterproof coiled material is increased, the relative molecular mass distribution of the ethylene-octene copolymer is narrow, high extrusion capacity is realized, production efficiency is greatly increased, and production cost is effectively reduced.
Description
One, technical field
What the present invention relates to is architectural waterproof material field, and what be specifically related to is a kind of sulfide type POE waterproof roll and production method thereof.
Two, background technology
At present, the best polymer coiled material of universally acknowledged over-all properties is sulfide type EPDM rubber waterproof rolling material, but glue material because terpolymer EP rubber belongs to nonpolar difficulty, thus cause sulfide type EPDM rubber waterproof rolling material to be difficult to widespread use because of adhesion problem always, progress along with science and technology has been born the macromolecular material of many excellent performances, wherein because of the molecular structure of POE and terpolymer EP rubber similar and be able to apply in water-proof material, some open source literatures also disclose the technology of some this respects in recent years, such as:
1, Chinese patent ZL98102553.6,: patent name is: " a kind of thermoplastic rubber-type water-proof coiled material " this invention proposes a kind of thermoplastic rubber-type water-proof coiled material, take thermoplastic elastomer as the rubber-type water-proof coiled material of matrix, employing POE is base rubber, and its composition parts by weight are: POE: 100 parts; Packing strengthening agent: 8.8 ~ 223 parts; Softening softening agent: 1.7 ~ 100 parts; Anti-aging agent: 0.5 ~ 4 part; 5 ~ 7.5 parts, activator can also be added; Linking agent: 0.05 ~ 0.7 part; Produce this rubber-type water-proof coiled material and do not need sulfuration manufacturing procedure, the goods after the tailing in production process, waste material and use can be recycled, and construction joint can adopt heat bonding.Its ageing-resistant performance meets or exceeds EPDM rubber waterproof rolling material.
2, Chinese patent ZL201010167683.1: patent name is: " a kind of ethylene-octene copolymer waterproof coil and preparation method thereof ", this invention relates to a kind of waterproof product, be specially a kind of ethylene-octene copolymer waterproof coil and preparation method thereof, solve existing waterproof roll and cannot meet product property indices and the too high problem of formulation cost completely, by ethylene-octene copolymer, chlorinatedpolyethylene, linear low density polyethylene, fill toughener, softening softening agent, phenolic antioxidant, thermo-stabilizer, lubricant and photostabilizer are made, various raw material is mixed, stir, adopt plastics processing mill, twin-roll machine and dicing machine granulation successively, pellet is dropped into single screw extrusion machine to extrude and through mould molding, molding mass is dropped into three roller cooling embossing machine roll-ins and go out waterproof roll.Both the distinctive pliability of rubber and elongation, rebound resilience had been remained, remain again the fracture tensile strength that LLDPE is higher, integral sheet pliability, planeness, planeness are good, performance index exceed national standard and Ministry of Railways's related standards, ageing-resistant performance, physicals and processing characteristics are all more excellent, and production cost is low.
3, Chinese patent ZL201210196189.7, patent name is: " thermo-welding overlays production formula and the technique of wet paving selfadhesive modified by maleic acid anhydride graft POE waterproof roll ", the production formula that this invention provides a kind of thermo-welding to overlay wet paving selfadhesive modified by maleic acid anhydride graft POE waterproof roll and technique, production technique is: by formula rate, all raw material is added in Banbury mixer, the banburying time is 15min, banburying temperature is 110-130 DEG C, makes it evenly mixing, blowing; 560 mills carried out down glue, be cooled to≤90 DEG C after lower bar, through rubber strainer impurity screening, thin-pass, mixing in 450 mills, mixing evenly after carry out lower bar; Extruder for shaping, the coiled material after shaping through the endless vulcanization tank of 20 meters long 170 DEG C, sulfuration under the condition of 0.3MPa; It is surface layer that modified by maleic acid anhydride graft PCE layer covers polypropylene fibre, terylene or acrylic fibers; Advantage is: have the high strength of plastics, thermoplastification melting property, have the characteristic of POE simultaneously, improve cohesive strength.
The technical scheme reported in above-mentioned open source literature 1,2 is that the method for employing unvulcanised is extruded, calendering formation; Although performance index have exceeded the standard of country and the Ministry of Railways, its because of molecular chain completely crosslinked; That material still presents is hot plastic state; Thermal stability is poor.In open source literature 3, the technical scheme of report adopts the method for modified by maleic acid anhydride graft POE sulfuration to extrude sulfidization molding, and the present inventor has consulted a large amount of documents and done little compatibility test many times; It is to make the molecular chain of modified by maleic acid anhydride graft POE crosslinked that theory and practice all demonstrates sulfur cross-linking system; Although the POE of Non-crosslinked has high strength and the weldability energy of outstanding plastics; But it is good that its heat resisting temperature and thermal stability can not show a candle to sulfuration terpolymer EP rubber.
Three, summary of the invention
An object of the present invention is to provide a kind of sulfide type POE waterproof roll, this sulfide type POE waterproof roll can not realize being cross-linked completely for the molecular chain solving current ethylene-octene copolymer waterproof coil, that material still presents is hot plastic state, the problem that thermal stability is poor; Another object of the present invention is to provide the production method of this sulfide type POE waterproof roll.
The technical solution adopted for the present invention to solve the technical problems is: this sulfide type POE waterproof roll comprises basic unit, base rubber take POE as main raw material, and other subsidiary material comprise and extrude carbon black, calcium carbonate, superfine talcum powder, polyoxyethylene glycol, anti-aging agent soon; Above-mentioned each component is counted by weight, and with POE 100 parts for benchmark, the content of other component is:
In such scheme, subsidiary material also comprise chlorinatedpolyethylene, and its content is 10 ~ 30 parts; Production cost of the present invention can be reduced like this.
In such scheme, subsidiary material comprise hexenoic acid ethylene copolymer, and its content is 5 ~ 25 parts, to reduce production cost of the present invention.
In such scheme, subsidiary material comprise terpolymer EP rubber, and its content is 10 ~ 50 parts, to reduce the hardness of product.
The production method of above-mentioned sulfide type POE waterproof roll, adopts and extrudes endless vulcanization explained hereafter, first POE rubber unvulcanizate is dropped into extruder for shaping; Shaping film enters sulfurizing pot vulcanization after measuring thickness device, trimming device; Coiled material after sulfuration is that continuous synchronization completes through cooling, inspection, numeration, curling packaging; Quantity-produced linear velocity is 3 ~ 8m/min, specific as follows:
A. glue is refined,
(1), by raw material each component put into by weight percentage and carry out mixing in Banbury mixer, melting temperature controls at 110 ~ 130 DEG C, mixing time 4 ~ 10 minutes;
(2), by being fed in Q560 mill of good for banburying rubber unvulcanizate carry out supplementary mixing and heat radiation, during rubber unvulcanizate exothermic temperature to 80 ~ 90 DEG C, shaping carries out next process,
B. glue is filtered,
(1), by mixing adhesive tape send into Q250 rubber strainer filter glue, filter screen is 80 orders, head temperature 92 DEG C; Body temperature 65 DEG C, extruder temperature 40 DEG C;
(2), the rubber unvulcanizate of mechanical impurity drops in Q450 mill and dispels the heat after filtering; Play film during rubber unvulcanizate exothermic temperature to 50 ~ 60 DEG C to weigh to the weight adding sulphur requirement;
C. sulphur and cooling is added,
(1), by the sizing material filtered deliver in Q450 mill and add vulcanizing agent and linking agent, when adding vulcanizing agent and linking agent, roller temperature control is < 50 DEG C, roll spacing 3 ~ 5 millimeters; To add after sulphur thin-pass three times; During thin-pass, roll spacing should control at 0.2 ~ 0.5 millimeter;
(2), will the glue stuff compounding shaping after sulphur be added, and cool and enter after parking twenty four hours and extrude vulcanization process;
D, sulfuration
Mixing adhesive tape dropped in forcing machine, the shaping film of forcing machine is after measuring thickness device and trimming device trimming fixed width; Enter vulcanizing boiler and carry out endless vulcanization; Vulcanizing boiler temperature control 165 ~ 170 DEG C, pressure-controlling in 0.2 ~ 0.3MPa, vulcanization line speed control at 3 ~ 8 ms/min;
E. after sulfuration, coiled material is shaped through refrigerating unit, and the coiled material after cooling and shaping is checked through rear haulage to verifying attachment, count, is finally packaged as finished product coiled material by crimping device rolling.
Beneficial effect:
1, in the present invention ethylene-octene copolymer after dicumyl peroxide is crosslinked, the molecular chain that can realize ethylene-octene copolymer waterproof coil is completely crosslinked, improve the thermal stability of waterproof roll, simultaneously because ethylene-octene copolymer relative molecular mass distribution is narrow, so it has preferably mobility can realize high extrusion capacity, significantly improve production efficiency, effectively must reduce production cost.
2, the present invention is in over-all properties; Ethylene-octene copolymer after dicumyl peroxide is crosslinked, except hardness is higher, wear resistance lower slightly except, all other physicalies are all better than ethylene-propylene rubber(EPR).
3, the present invention is in economic benefit; Ethylene-propylene rubber(EPR) price is higher all the time; And price volalility is larger, and ethylene-octene copolymer is moderate, fluctuation little, and major part all can exceed ethylene-propylene rubber(EPR) simultaneously; Ethylene-octene copolymer can be used as the equivalent material of ethylene-propylene rubber(EPR) and becomes material indispensable in macromolecular material in the future.
4, the present invention is in thermo-welding performance; Although ethylene-octene copolymer molecule is after peroxide crosslinking, but its natural characteristics major part still maintains, though its sweating soldering performance is good not as good as uncrosslinked, but adopt high temperature thermal wedge pressure welding still can obtain very high heat seal strength, the resistance toheat of weld seam is the same with body, and this feature is that other material cannot match in excellence or beauty with it.
Four, embodiment
Embodiment 1:
This sulfide type POE waterproof roll comprises basic unit, and base rubber take POE as main raw material, counts by weight, and with ethylene-octene copolymer 100 parts for benchmark, the content of other component is:
The production method of the present embodiment sulfide type POE waterproof roll, adopts and extrudes endless vulcanization explained hereafter, first POE rubber unvulcanizate is dropped into extruder for shaping; Shaping film enters sulfurizing pot vulcanization after measuring thickness device, trimming device; Coiled material after sulfuration is that continuous synchronization completes through cooling, inspection, numeration, curling packaging; Quantity-produced linear velocity is 3 ~ 8m/min.Specific as follows:
A. glue is refined,
(1), by raw material each component put into by weight percentage and carry out mixing in Banbury mixer, melting temperature controls at 110 ~ 130 DEG C, mixing time 4 ~ 10 minutes;
(2), by being fed in Q560 mill of good for banburying rubber unvulcanizate carry out supplementary mixing and heat radiation, during rubber unvulcanizate exothermic temperature to 80 ~ 90 DEG C, shaping carries out next process,
B. glue is filtered,
(1), by mixing adhesive tape send into Q250 rubber strainer filter glue, filter screen is 80 orders, head temperature 92 DEG C; Body temperature 65 DEG C, extruder temperature 40 DEG C;
(2), the rubber unvulcanizate of mechanical impurity drops in Q450 mill and dispels the heat after filtering; Play film during rubber unvulcanizate exothermic temperature to 50 ~ 60 DEG C to weigh to the weight adding sulphur requirement;
C. sulphur and cooling is added,
(1), by the sizing material filtered deliver in Q450 mill and add promotor and sulphur, when adding promotor and sulphur, roller temperature control is < 50 DEG C, roll spacing 3 ~ 5 millimeters; To add after sulphur thin-pass three times; During thin-pass, roll spacing should control at 0.2 ~ 0.5 millimeter;
(2), will the glue stuff compounding shaping after sulphur be added, and cool and enter after parking twenty four hours and extrude vulcanization process;
D, sulfuration
Mixing adhesive tape dropped in forcing machine, the shaping film of forcing machine is after measuring thickness device and trimming device trimming fixed width; Enter vulcanizing boiler and carry out endless vulcanization; Vulcanizing boiler temperature control 165 ~ 170 DEG C, pressure-controlling in 0.2 ~ 0.3MPa, vulcanization line speed control at 3 ~ 8 ms/min.
E. after sulfuration, coiled material is shaped through refrigerating unit, and the coiled material after cooling and shaping is checked through rear haulage to verifying attachment, count, is finally packaged as finished product coiled material by crimping device rolling.
Embodiment 2:
This sulfide type POE waterproof roll comprises basic unit, and base rubber take POE as main raw material, counts by weight, and with POE 100 parts for benchmark, the content of other component is:
The production method of the present embodiment sulfide type POE waterproof roll, adopts and extrudes endless vulcanization explained hereafter, first POE rubber unvulcanizate is dropped into extruder for shaping; Shaping film enters sulfurizing pot vulcanization after measuring thickness device, trimming device; Coiled material after sulfuration is that continuous synchronization completes through cooling, inspection, numeration, curling packaging; Quantity-produced linear velocity is 3 ~ 8m/min.Specific as follows:
A. glue is refined,
(1), by raw material each component put into by weight percentage and carry out mixing in Banbury mixer, melting temperature controls at 110 ~ 130 DEG C, mixing time 4 ~ 10 minutes;
(2), by being fed in Q560 mill of good for banburying rubber unvulcanizate carry out supplementary mixing and heat radiation, during rubber unvulcanizate exothermic temperature to 80 ~ 90 DEG C, shaping carries out next process,
B. glue is filtered,
(1), by mixing adhesive tape send into Q250 rubber strainer filter glue, filter screen is 80 orders, head temperature 92 DEG C; Body temperature 65 DEG C, extruder temperature 40 DEG C;
(2), the rubber unvulcanizate of mechanical impurity drops in Q450 mill and dispels the heat after filtering; Play film during rubber unvulcanizate exothermic temperature to 50 ~ 60 DEG C to weigh to the weight adding sulphur requirement;
C. sulphur and cooling is added,
(1), by the sizing material filtered deliver in Q450 mill and add promotor and sulphur, when adding promotor and sulphur, roller temperature control is < 50 DEG C, roll spacing 3 ~ 5 millimeters; To add after sulphur thin-pass three times; During thin-pass, roll spacing should control at 0.2 ~ 0.5 millimeter;
(2), will the glue stuff compounding shaping after sulphur be added, and cool and enter after parking twenty four hours and extrude vulcanization process;
D, sulfuration
Mixing adhesive tape dropped in forcing machine, the shaping film of forcing machine is after measuring thickness device and trimming device trimming fixed width; Enter vulcanizing boiler and carry out endless vulcanization; Vulcanizing boiler temperature control 165 ~ 170 DEG C, pressure-controlling in 0.2 ~ 0.3MPa, vulcanization line speed control at 3 ~ 8 ms/min.
E. after sulfuration, coiled material is shaped through refrigerating unit, and the coiled material after cooling and shaping is checked through rear haulage to verifying attachment, count, is finally packaged as finished product coiled material by crimping device rolling.
Embodiment 3:
This sulfide type POE waterproof roll comprises basic unit, and base rubber take POE as main raw material, counts by weight, and with POE 100 parts for benchmark, the content of other component is:
Embodiment 4:
This sulfide type POE waterproof roll comprises basic unit, and base rubber take POE as main raw material, counts by weight, and with POE 100 parts for benchmark, the content of other component is:
Embodiment 5:
This sulfide type POE waterproof roll comprises basic unit, and base rubber take POE as main raw material, counts by weight, and with POE 100 parts for benchmark, the content of other component is:
Embodiment 6:
This sulfide type POE waterproof roll comprises basic unit, and base rubber take POE as main raw material, counts by weight, and with POE 100 parts for benchmark, the content of other component is:
POE waterproof roll through producing raw material described in above-described embodiment carries out quantitative measurement, the standard performed during test is " GB18173.1-2012 ", wherein the 9th, 10 not in standard range, in table, numerical value is the measured value adopting high temperature thermal wedge pressure welding.Be below the measured value of standard value and the above embodiment of the present invention as following table:
In table, the physical performance index of waterproof roll of the present invention all exceedes the requirement in " GB18173.1-2012 " standard, and wherein comparatively outstanding is that tensile strength and tear strength index all improve more than 28% and 48% than standard-required.This terpolymer EP rubber when not improving material cost to touch the mark.And its higher soldered bonds, under stripping strength and shearing condition, binding property is also that terpolymer EP rubber can not be compared.
The above is only embodiments of the invention; but not be particularly limited to of the present invention; for those skilled in the art; multi-form variation or conversion also can be made on the basis of the above description in the basis understanding technique scheme, and the apparent variation of extending out thus or conversion are still in protection scope of the present invention.
Claims (5)
1. a sulfide type POE waterproof roll, it is characterized in that: this sulfide type POE waterproof roll comprises basic unit, base rubber take POE as main raw material, and other subsidiary material comprise and extrude carbon black, calcium carbonate, superfine talcum powder, polyoxyethylene glycol, anti-aging agent soon; Above-mentioned each component is counted by weight, and with POE 100 parts for benchmark, the content of other component is:
2. sulfide type POE waterproof roll according to claim 1, is characterized in that: described subsidiary material also comprise chlorinatedpolyethylene, and its content is 10 ~ 30 parts.
3. sulfide type POE waterproof roll according to claim 2, is characterized in that: described subsidiary material comprise ethylene vinyl acetate, and its content is 5 ~ 25 parts.
4. sulfide type POE waterproof roll according to claim 3, is characterized in that: described subsidiary material comprise terpolymer EP rubber, and its content is 10 ~ 50 parts.
5. the production method of a claim 1 or 2 or the sulfide type POE waterproof roll described in 3 or 4, it is characterized in that: the production method of this sulfide type POE waterproof roll, endless vulcanization explained hereafter is extruded in employing, first POE rubber unvulcanizate is dropped into extruder for shaping; Shaping film enters sulfurizing pot vulcanization after measuring thickness device, trimming device; Coiled material after sulfuration is that continuous synchronization completes through cooling, inspection, numeration, curling packaging; Quantity-produced linear velocity is 3 ~ 8m/min, specific as follows:
A. glue is refined,
(1), by raw material each component put into by weight percentage and carry out mixing in Banbury mixer, melting temperature controls at 110 ~ 130 DEG C, mixing time 4 ~ 10 minutes;
(2), by the rubber unvulcanizate that banburying is good be fed in Q560 mill and carry out supplementary mixing and heat radiation, during rubber unvulcanizate exothermic temperature to 80 ~ 90 DEG C, shaping carries out next process,
B. glue is filtered,
(1), by mixing adhesive tape send into Q250 rubber strainer filter glue, filter screen is 80 orders, head temperature 92 DEG C; Body temperature 65 DEG C, extruder temperature 40 DEG C;
(2), the rubber unvulcanizate of mechanical impurity drops in Q450 mill and dispels the heat after filtering; Play film during rubber unvulcanizate exothermic temperature to 50 ~ 60 DEG C to weigh to the weight adding sulphur requirement;
C. sulphur and cooling is added,
(1), by the sizing material filtered deliver in Q450 mill and add vulcanizing agent and linking agent, when adding vulcanizing agent and linking agent, roller temperature control is < 50 DEG C, roll spacing 3 ~ 5 millimeters; To add after vulcanizing agent and linking agent thin-pass three times; During thin-pass, roll spacing should control at 0.2 ~ 0.5 millimeter;
(2), will the glue stuff compounding shaping after sulphur be added, and cool and enter after parking twenty four hours and extrude vulcanization process;
D, sulfuration
Mixing adhesive tape dropped in forcing machine, the shaping film of forcing machine is after measuring thickness device and trimming device trimming fixed width; Enter vulcanizing boiler and carry out endless vulcanization; Vulcanizing boiler temperature control 165 ~ 170 DEG C, pressure-controlling in 0.2 ~ 0.3MPa, vulcanization line speed control at 3 ~ 8 ms/min;
E. after sulfuration, coiled material is shaped through refrigerating unit, and the coiled material after cooling and shaping is checked through rear haulage to verifying attachment, count, is finally packaged as finished product coiled material by crimping device rolling.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105504629A (en) * | 2015-12-29 | 2016-04-20 | 慈溪卡希尔密封材料有限公司 | Asbestos-free fiber compressing board and preparation method |
| CN106366398A (en) * | 2016-08-27 | 2017-02-01 | 潍坊市宏源防水材料有限公司 | Peroxide cross-linked polyolefin waterproof coiled material and preparation technology thereof |
| CN106738425A (en) * | 2017-01-22 | 2017-05-31 | 中国铁道科学研究院铁道建筑研究所 | Rubber process units comprising information Jian Zao mechanisms |
| CN108546358A (en) * | 2018-03-30 | 2018-09-18 | 解飞 | A kind of vulcanization type POE waterproof rolls and its production method |
| CN114907662A (en) * | 2022-06-14 | 2022-08-16 | 广东创永佳新材料有限公司 | Novel wear-resistant corrosion-resistant engineering plastic material and preparation method thereof |
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| CN103254494A (en) * | 2013-05-04 | 2013-08-21 | 忻州市四方铁路器材有限公司 | Flame-retardant chlorinated polyethylene waterproof coil and production process thereof |
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| CN114907662A (en) * | 2022-06-14 | 2022-08-16 | 广东创永佳新材料有限公司 | Novel wear-resistant corrosion-resistant engineering plastic material and preparation method thereof |
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